Development of large-area CIGS modules

It is a big challenge for all thin-film PV technologies to exhaust the high potential of cost reduction, which is beyond controversy. For Cu(In,Ga)Se₂ (CIGS) based PV modules, which have the highest efficiency potential among thin-film technologies, a productive industrial process technology has been not demonstrated up to now.In the ZSW line, the maximum efficiency for 30 cm×30 cm was close to 13% (11% in average) at a high yield. In several batches, hundreds of modules were processed and characterized. Process statistics are described.First results of film depositions and processing on large area from the Wuerth Solar pilot line are presented. The concept for the integrated module line will be discussed. First modules in the square meter range are demonstrated with efficiencies >8%.     

CuInSe2 photovoltaic modules

This paper reviews the status of CuInSe₂ (CIS) module development. The potential of CIS for high power, thin film photovoltaic modules is demonstrated by the achievement of 14.1% active area cell efficiencies and unlaminated module power outputs of 10.5 W (11.2% aperture efficiency) on 940 cm² modules and 37.8 W (9.7% aperture efficiency) on 3900 m² modules. The definition of 0.4 m² CIS module pilot production is progressing.     

New materials and deposition techniques for highly efficient silicon thin film solar cells

This paper reviews recent efforts to provide the scientific and technological basis for cost-effective and highly efficient thin film solar modules based on amorphous (a-Si:H) and microcrystalline (μc-Si:H) silicon. Textured ZnO:Al films prepared by sputtering and wet chemical etching were applied to design optimised light-trapping schemes. Necessary prerequisite was the detailed knowledge of the relationship between film growth, structural properties and surface morphology obtained after etching. High rate deposition using plasma enhanced chemical vapour deposition at 13.56 MHz plasma excitation frequency was developed for μc-Si:H solar cells yielding efficiencies of 8.1% and 7.5% at deposition rates of 5 and 9 Å/s, respectively. These μc-Si:H solar cells were successfully up-scaled to a substrate area of 30×30 cm² and applied in a-Si:H/μc-Si:H tandem cells showing initial test cell efficiencies up to 11.9%.     

A glass frit-sealed dye solar cell module with integrated series connections

As the dye solar cell (DSC) technology progresses from laboratory-scale to large-area applications, long-term stability is one major obstacle. Especially for large-area DSC modules, stability is often a matter of hermetic sealing both between cells and for the whole module. Here we suggest glass frit as sealing material. Glass frit is thermally, mechanically and chemically very stable and can be applied via screen printing.DSC modules of 30×30 cm² with a glass frit as primary sealing material have been produced.It was shown that glass frit is applicable for the upscaling of the DSC technology to large areas. The thermal stability of the glass frit sealing and the integrated series connections was verified in a thermal cycling from −40 to 80 °C.The colouration process has been scaled up to 30×30 cm² by pumping the dye solution through the module using only two filling holes. By heating the module to 70 °C the filling of the module with electrolytes based on high viscous ionic liquids was demonstrated.     

All solid-state electrochromic devices with gelatin-based electrolyte

6×8 cm² electrochromic devices (ECDs) with the configuration K-glass/EC-layer/electrolyte/ion-storage (IS) layer/K-glass, have been assembled using Nb₂O₅:Mo EC layers, a (CeO₂)_0.81–TiO₂ IS-layer and a new gelatin electrolyte containing Li⁺ ions. The structure of the electrolyte is X-ray amorphous. Its ionic conductivity passed by a maximum of 1.5×10⁻⁵ S/cm for a lithium concentration of 0.3 g/15 ml. The value increases with temperature and follows an Arrhenius law with an activation energy of 49.5 kJ/mol. All solid-state devices show a reversible gray coloration, a long-term stability of more than 25,000 switching cycles (±2.0 V/90 s), a transmission change at 550 nm between 60% (bleached state) and 40% (colored state) corresponding to a change of the optical density (ΔOD=0.15) with a coloration efficiency increasing from 10 cm²/C (initial cycle) to 23 cm²/C (25,000th cycle).     

Effect of proton irradiation on electrical properties of CuInSe2 thin films

High-energy proton irradiation (380 keV and 1 MeV) on the electrical properties of CuInSe₂ (CIS) thin films has been investigated. The samples were epitaxially grown on GaAs (0 0 1) substrates by Radio Frequency sputtering. As the proton fluence exceeded 1×10¹³ cm⁻², the carrier concentration and mobility of the CIS thin films were decreased. The carrier removal rate with proton fluence was estimated to be about 1000 cm⁻¹. The electrical properties of CIS thin films before and after irradiation were studied between 80 and 300 K. From the temperature dependence of the carrier concentration in CIS thin films, we found N_D=9.5×10¹⁶ cm⁻³, N_A=3.7×10¹⁶ cm⁻³ and E_D=21 meV from the fitting to the experimental data on the basis of the charge balance equation. After irradiation, a defect level was created, and N_T=1×10¹⁷ cm⁻³ for a fluence of 3×10¹³ cm⁻², N_T=5.7×10¹⁷ cm⁻³ for a fluence of 1×10¹⁴ cm⁻² and E_T=95 meV were also obtained from the same fitting. The new defect, which acted as an electron trap, was due to proton irradiation, and the defect density was increased with proton fluence.     

Reduction of defects of polycrystalline silicon thin films by heat treatment with high-pressure H2O vapor

An improvement of electrical properties of pulsed laser crystalllized silicon films was achieved by simple heat treatment with high-pressure H₂O vapor. The electrical conductivity of 7.4×10¹⁷ cm⁻³ phosphorus-doped 50-nm-thick pulsed laser crystallized silicon films was markedly increased from 1.6×10⁻⁵ S/cm (as crystallized) to 2 S/cm by heat treatment at 270°C for 3 h with 1.25×10⁶ Pa H₂O vapor because of reduction of density of defect states localized at grain boundaries. Spin density was reduced from 1.7×10¹⁸ cm⁻³ (as crystallized) to 1.2×10¹⁷ cm⁻³ by heat treatment at 310°C for 3 h with 1.25×10⁶ Pa H₂O vapor.     

High-efficiency OECO Czochralski-silicon solar cells for mass production

To improve the economy of photovoltaics, efficiencies of solar cells have to be drastically increased without using complex technologies. This work demonstrates that with the obliquely evaporated contact metal-insulator-semiconductor (MIS)-n⁺p solar cell structure recently developed at ISFH efficiencies exceeding 21% can be obtained using only four simple fabrication steps: (i) mechanical surface grooving, (ii) P-diffusion, (iii) oblique vacuum evaporation of Al, and (iv) plasma silicon nitride deposition. Cell design and processing sequences are outlined together with the importance of MIS contacts as both low-cost and high efficiency features. The custom-made pilot line equipment for mass production of 20% efficient 10×10 cm² Cz silicon solar cells including Ga doped wafers is described.     

Recent progress in scaling up highly efficient Zn(S,O)/Cu-chalcopyrite thin film solar cells and modules at HZB

In the present contribution we report on recent work covering Zn(S,O) buffer as heterojunction partner layer applied to pilot line low-gap Cu(In,Ga)(SSe)₂ (CIGSSe, E_g = 1.03 eV) and production scale wide-gap CuInS₂ (CIS, E_g = 1.54 eV). We highlight the crucial role that the processing control of the Zn(S,O) plays for the fabrication of Cu-chalcopyrite solar cells and modules. The analytical information obtained by the correlation with state-of-the art high resolution Transmission electron microscopy, X-ray photoemission and Auger spectroscopy (XPS and XAES) as well as L-edge XAS are discussed. A large number of efficient laboratory-scale solar cells and monolithically interconnected prototype CIGSSe and CIS modules are produced. The efficiencies are comparable to the CdS base line references or even higher. The electrical, electronic properties and the emerging phenomena in Cd-free devices such as light soaking are discussed.     

Physical properties of Bi doped CdTe thin films grown by the CSVT method

A study of the physical properties of CdTe thin films doped with Bi is presented. CdTe:Bi thin films were deposited by the close space vapor transport (CSVT) technique using powdered CdTe:Bi crystals grown by the vertical Bridgman method. CdTe:Bi crystals were obtained with nominal Bi doping concentrations varying in the 1×10¹⁷–8×10¹⁸ cm⁻³ range. The physical properties of CdTe:Bi thin films were studied performing photoluminescence, X-ray, SEM, photoacoustic spectroscopy and resistivity measurements. We observed a decrease of the resistivity values of CdTe:Bi films with the Bi content as low as 6×10⁵ Ω-cm for Bi concentrations of 8×10¹⁸ cm⁻³. These are meaningful results for CdTe-based solar cells.     

Pyrite (FeS2) thin films prepared by spray method using FeSO4 and (NH4)2Sx

A simple spray method for the preparation of pyrite (FeS₂) thin films has been studied using FeSO₄ and (NH₄)₂S_x as precursors for Fe and S, respectively. Aqueous solutions of these precursors are sprayed alternately onto a substrate heated up to 120°C. Although Fe–S compounds including pyrite are formed on the substrate by the spraying, sulfurization of deposited films is needed to convert other phases such as FeS or marcasite into pyrite. A single-phase pyrite film is obtained after the sulfurization in a H₂S atmosphere at around 500°C for 30 min. All pyrite films prepared show p-type conduction. They have a carrier concentration (p) in the range 10¹⁶–10²⁰ cm⁻³ and a Hall mobility (μ_H) in the range 200–1 cm²/V s. The best electrical properties (p=7×10¹⁶ cm⁻³, μ_H=210 cm²/V s) for a pyrite film prepared here show the excellence of this method. The use of a lower concentration FeSO₄ solution is found to enhance grain growth of pyrite crystals and also to improve electrical properties of pyrite films.     

Synthesis and characterization of aluminum-doped CdO thin films by sol–gel process

Aluminum-doped cadmium oxide (CdO:Al) thin films are deposited on glass substrates by the sol–gel dip-coating method, taking cadmium acetate dihydrate as the precursor material. Aluminum nitrate has been taken as a source of Al-dopant. XRD pattern reveals the good crystallinity of CdO thin films. SEM micrograph showed the presence of faceted crystallites. Optical study shows 40–85% transparency with a bandgap value lying in the range 2.76–2.52 eV, depending upon the Al content in the films. Optimum percentage of Al was 5.22 for a maximum room temperature conductivity of 2.81×10³ (Ω cm)⁻¹. Hall measurement confirmed that the material is of n-type, with mobility and carrier concentrations lying in the range 413–14.7 cm²/V s, and 3.4×10¹⁹–8.11×10²⁰ cm⁻³, when percentage of Al varies in the range 1.32–7.24.     

A new generation of crystalline silicon solar cells: Simple processing and record efficiencies for industrial-size devices

In contrast to the general opinion that very high efficiencies can only be obtained using complex processing, with the novel technologically simple and environmentally sound obliquely evaporated contact (OECO) type solar cell efficiencies exceeding 21% could be obtained without applying masks or photolithography. Two different approaches of OECO cells using MIS contacts and exclusively Al as metallization are discussed: (i) with a diffused n⁺-emitter (MIS-n⁺p) and (ii) with an inversion layer emitter (MIS-IL). The most important results particularly for industrial production are efficiencies of 19% and 20% for simply to fabricate 10×10 cm² OECO cells on commercial CZ-Si and FZ-Si, respectively. These are the highest efficiencies ever reported for solar cells of industrial size.     

Effects of water in phthalocyanine layers

The molecular water concentration inside zinc phthalocyanine (ZnPc) thin films was measured. After exposure to air, gas effusion experiments show that the ZnPc layers contain (1.7±0.4)×10²⁰ water molecules per cm³, which corresponds to 1 H₂O per 10 ZnPc units. We can distinguish a mobile and an immobilized population of H₂O in ZnPc films. The mobile part effuses out at room temperature when exposing the films to a low pressure of 10⁻² mbar, whereas temperature activation is needed to reach a complete out-diffusion of water. The effusion process was observed to proceed with a diffusion coefficient D_H2O of (1.3±0.3)×10⁻¹⁰ cm² s⁻¹ at 296 K. The rate of water effusion directly correlates with the timescale of the decrease of surface conductivity when exposing the layers to an equally low pressure. This indicates the existence of an electrically active surface layer of water molecules, which is refilled from the bulk of water molecules during the effusion process.     

Imidazolium-based ionic liquid derivatives for application in electrochromic devices

Novel proton-conducting electrolytes were prepared from the sol–gel precursor 1-[3-(trimethoxy-λ⁴-silyl)propyl]imidazole with the addition of either trifluoroacetic or acetic acid. The presence of trimethoxysilyl groups enabled the solvolysis and condensation reactions of silsesquioxane species. IR spectroscopy revealed that more cube-like species formed in the electrolyte prepared from trifluoroacetic acid, while cube- and ladder-like silsesquioxanes were present in the electrolyte with acetic acid. This assignation was independently confirmed by ²⁹Si NMR analyses revealing the T³ signals of trisiloxane bonding. IR spectroscopy also pointed to the formation of hydrogen bonding in the latter electrolyte, since the frequencies of the observed bands at 1710, 1409, and 1272 cm⁻¹ approached those of acetic acid. In contrast, the IR bands at 1662, 1204, and 1130 cm⁻¹ confirmed the existence of trifluoroacetate anions in the case when the electrolyte was prepared from trifluoroacetic acid. The presence of free trifluoroacetate anions contributed to the moderately higher specific conductivity of this electrolyte (4.6×10⁻⁵ S/cm) compared to that of acetic acid (1.6×10⁻⁵ S/cm). The specific conductivity of the electrolytes could be further increased by the addition of a lithium salt. All electrolytes were employed in electrochromic devices with optically active WO₃ and various inorganic counter-electrodes (CeVO₄, V₂O₅, Ti/V-oxide). Photopic transmittance changes from 30% to 40% were achieved.     

The spray-ILGAR (ion layer gas reaction) method for the deposition of thin semiconductor layers: Process and applications for thin film solar cells

The spray Ion Layer Gas Reaction (ILGAR) process starts with ultrasonic nebulisation of the precursor solution, e.g. InCl₃/ethanol for our successful buffer material In₂S₃. In an aerosol assisted chemical vapour deposition (AACVD) type reaction an In(O,OH,Cl) film is deposited on a heated substrate and is subsequently converted to In₂S₃ by H₂S gas. The cycle of these steps is repeated until the required layer thickness is obtained. The robust and reproducible process allows a wide control of composition and morphology.Results of this “spray-ILGAR” method with respect to process, material properties and its application depositing the buffer layer in chalcopyrite solar cells are reviewed. New aspects such as the investigation of the complex chemical mechanism by mass spectrometry, the process acceleration by the addition of H₂S gas to the aerosol, the controlled deposition of ZnS nano-dot films and finally the latest achievements in process up-scaling are also included.Solar cells based on industrial Cu(In,Ga)(S,Se)₂ absorbers (Avancis GmbH) with a Spray-ILGAR In₂S₃ buffer reached 14.7% efficiency (certified) and 15.3% with a ZnS/In₂S₃ bi-layer buffer comparable to reference cells using standard CdS buffer layers deposited by chemical bath deposition (CBD).The quasi-dry, vacuum-free ILGAR method for In₂S₃ buffer layers is well suited for industrial in-line production and is capable of not only replacing the standard buffer material (the toxic CdS) but also the often slow CBD process. A tape coater for 10 cm wide steel tape was constructed. It was shown that In₂S₃ layers could be produced with an indium yield better than 30% and a linear production speed of 1m/min. A roll-to-roll pilot production line for electrochemically deposited Cu(In,Ga)Se₂ with ILGAR buffer is running in industry (CIS-Solartechnik, Hamburg). A 30x30 cm² prototype of an ILGAR in-line coater developed by Singulus and Helmholtz Zentrum Berlin is currently being optimised. First 30×30 cm² encapsulated modules achieved efficiencies up to 13.0% (CdS buffered reference 13.3%).     

Radiation resistant AlGaAs/GaAs concentrator solar cells with internal Bragg reflector

The problem of increasing efficiency, reliability and radiation resistance of solar cells based on AlGaAs/GaAs heterostructures can be solved by using an internal Bragg reflector. The Bragg reflector as a back surface reflector and as a back surface potential barrier which allows to conserve the high photosensitivity in the long- and middle-wavelength parts of the spectrum after electron and proton irradiation. The effect of base doping and base thickness on the radiation resistance of AlGaAs/GaAs solar cells with the internal Bragg reflector has been investigated. Concentrator solar cells efficiency and related parameters before and after 3 MeV electron irradiation at the fluence up to 3×10¹⁵ cm⁻² are represented. A base doping level of 1×10¹⁵ cm⁻³ and base thickness in the range 1.1–1.6 μm give an EOL AM0 efficiency of 15.8% (BOL–22%) at 30 Suns concentration after exposure to 1×10¹⁵ cm⁻² electron fluence. This EOL efficiency is among the highest reported for GaAs single-junction concentrator cells under AM0 conditions. Making the base doping level lower and the base thinner allows retaining a j_EOL/j_BOL ratio of 0.96 upon exposure up to 3×10¹⁵e/cm² 3 MeV electron fluence. These results are additionally supported by the modeling calculations of the relative damage coefficient.     

Microcrystalline silicon thin film solar modules on glass

We developed microcrystalline silicon (μc-Si:H) thin film solar modules on textured ZnO-coated glass. The single junction (p–i–n) cell structure was prepared by plasma-enhanced chemical vapour deposition (PECVD) at substrate temperatures below 250 °C. Front ZnO and back contacts were prepared by sputtering. A process for the monolithic series connection of μc-Si:H cells by laser scribing was developed. These microcrystalline p–i–n modules showed aperture area efficiencies up to 8.3% and 7.3% on aperture areas of 64 and 676 cm², respectively. The temperature coefficient of the efficiency was −0.4%/K.     

Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin films

Thin films of tungsten oxide (WO₃) were deposited onto glass, ITO coated glass and silicon substrates by pulsed DC magnetron sputtering (in active arc suppression mode) of tungsten metal with pure oxygen as sputter gas. The films were deposited at various oxygen pressures in the range 1.5×10⁻²−5.2×10⁻² mbar. The influence of oxygen sputters gas pressure on the structural, optical and electrochromic properties of the WO₃ thin films has been investigated. All the films grown at various oxygen pressures were found to be amorphous and near stoichiometric. A high refractive index of 2.1 (at λ=550 nm) was obtained for the film deposited at a sputtering pressure of 5.2×10⁻² mbar and it decreases at lower oxygen sputter pressure. The maximum optical band gap of 3.14 eV was obtained for the film deposited at 3.1×10⁻² mbar, and it decreases with increasing sputter pressure. The decrease in band gap and increase in refractive index for the films deposited at 5.2×10⁻² mbar is attributed to the densification of films due to ‘negative ion effects’ in sputter deposition of highly oxygenated targets. The electrochromic studies were performed by protonic intercalation/de-intercalation in the films using 0.5 M HCl dissolved in distilled water as electrolyte. The films deposited at high oxygen pressure are found to exhibit better electrochromic properties with high optical modulation (75%), high coloration efficiency (CE) (141.0 cm²/C) and less switching time at λ=550 nm; the enhanced electrochromism in these films is attributed to their low film density, smaller particle size and larger thickness. However, the faster color/bleach dynamics is these films is ascribed to the large insertion/removal of protons, as evident from the contact potential measurements (CPD) using Kelvin probe. The work function of the films deposited at 1.5 and 5.2×10⁻² mbar are 4.41 and 4.30 eV, respectively.     

A thin-film solar cell of high-quality -FeSi2/Si heterojunction prepared by sputtering

High-quality (1 1 0)/(1 0 1)-oriented epitaxial β-FeSi₂ films were fabricated on Si (1 1 1) substrate by the sputtering method. The critical feature was the formation of a high-quality thin β-FeSi₂ template buffer layer on Si (1 1 1) substrate at low temperature. It was demonstrated that the template is very important for the epitaxial growth of thick β-FeSi₂ films and for the blocking of Fe diffusion into the Si at the β-FeSi₂/Si interface. Hall effect measurements for β-FeSi₂ films showed n-type conductivity, with residual electron concentration around 2.0 × 10¹⁷ cm⁻³ and mobility of 50–400 cm²/V s. A prototype thin-film solar cell was fabricated by depositing n-β-FeSi₂ on p-Si (1 1 1). Under 100 mW/cm² sunlight, an energy conversion efficiency of 3.7%, with an open-circuit voltage of 0.45 V, a short-circuit current density of 14.8 mA/cm² and a fill factor of 0.55, was obtained.